CN108172828B - Fluoride ion all-solid-state battery - Google Patents

Fluoride ion all-solid-state battery Download PDF

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CN108172828B
CN108172828B CN201711231760.3A CN201711231760A CN108172828B CN 108172828 B CN108172828 B CN 108172828B CN 201711231760 A CN201711231760 A CN 201711231760A CN 108172828 B CN108172828 B CN 108172828B
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electrode layer
fluoride
negative electrode
fluoride ion
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CN108172828A (en
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井手一人
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Toyota Motor Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • C01F17/00—Compounds of rare earth metals
    • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
    • C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a fluoride ion all-solid-state battery. The present disclosure addresses the problem of providing a fluoride ion all-solid-state battery having good capacity characteristics. In the present disclosure, the above-mentioned problems are solved by providing a fluoride ion all-solid battery which is a fluoride ion all-solid battery having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer, characterized in that the negative electrode layer contains a metal fluoride containing an M1 element, an M2 element, and an F element, and the M1 element is at-2.5V (vs2) A metal element which is fluorinated and defluorinated at the above potential, wherein the M2 element is at-2.5V (vs. Pb/PbF)2) A metal element which is not fluorinated or defluorinated at the above potential, wherein the M2 element has a fluoride ion conductivity of 1X 10 at 200 ℃ when a fluoride is formed‑4Metal elements of S/cm or more.

Description

Fluoride ion all-solid-state battery
Technical Field
The present disclosure relates to a fluoride ion all-solid-state battery having good capacity characteristics.
Background
As a battery having a high voltage and a high energy density, for example, a Li-ion battery is known. The Li-ion battery is a battery using a cation group of a reaction between Li ions and a positive electrode active material and a reaction between Li ions and a negative electrode active material. On the other hand, as an anion-based battery, a fluoride ion all-solid-state battery utilizing a reaction of fluoride ions is known.
For example, non-patent document 1 discloses a method using an active material (e.g., BiF)3、CuF2) And a negative electrode mixed material obtained by mixing a solid electrolyte and a conductive material. Non-patent document 1 shows BiF as an example3La is mixed with0.9Ba0.1F2.9As solid electrolyte, acetylene blackA negative electrode hybrid material that is a conductive material. In addition, for example, patent document 1 discloses a technique of adding a polymer or glass that suppresses battery destruction caused by shrinkage expansion of an electrode to at least one of a positive electrode, a solid electrolyte, and a negative electrode of a fluoride ion all-solid battery.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5517451
Non-patent document
Non-patent document 1: M.A. Reddy et al, "Batteries based on fluoride short", journal of Material Chemistry 21(2011), p.17059-17062
Disclosure of Invention
Problems to be solved by the invention
In recent years, with the increase in performance of batteries, further improvement in capacity characteristics of batteries has been demanded. The present disclosure has been made in view of the above circumstances, and a main object thereof is to provide a fluoride ion all-solid-state battery having good capacity characteristics.
Means for solving the problems
In order to solve the above problems, the present inventors have made extensive studies and, as a result, have come to recognize that: by using a metal fluoride containing a specific metal element for the negative electrode layer, a fluoride ion all-solid battery having good capacity characteristics can be obtained. The present disclosure is an invention based on the above recognition.
In the present disclosure, there is provided a fluoride ion all-solid battery which is a fluoride ion all-solid battery having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer, characterized in that the negative electrode layer contains a metal fluoride containing an M1 element, an M2 element, and an F element, and the M1 element is at-2.5V (vs2) A metal element which is fluorinated and defluorinated at the above potential, wherein the M2 element is at-2.5V (vs. Pb/PbF)2) A metal element which is not fluorinated or defluorinated at the above potential, wherein the M2 element is a fluoride ion transfer at 200 ℃ in the case where a fluoride is formedThe permeability becomes 1X 10-4Metal elements of S/cm or more.
According to the present disclosure, since the negative electrode layer contains the metal fluoride including the M1 element, the M2 element, and the F element, a metal (active material) of the M1 element and a metal fluoride (solid electrolyte) including the M2 element and the F element can be formed in a state of being dispersed at an atomic level in the negative electrode layer at the time of charging. On the other hand, since the electron conductivity of the metal of the element M1 is high, the fluoride ion conductivity of the metal fluoride containing the element M2 and the element F is high, and both are dispersed at the atomic level, a fluoride ion battery having good capacity characteristics can be obtained.
In the above disclosure, it is preferred that the metal fluoride has a chemical formula of M1xM2(1-x)Fy(x is more than or equal to 0.75 and less than or equal to 0.95, and y is a real number more than 0).
In the present disclosure, there is provided a fluoride ion all-solid battery which is a fluoride ion all-solid battery having a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer, characterized in that the negative electrode layer contains a metal of an M1 element and a metal fluoride containing an M2 element and an F element, the metal of the M1 element and the metal fluoride are dispersed at an atomic level, and the M1 element is at-2.5V (vs2) A metal element which is fluorinated and defluorinated at the above potential, wherein the M2 element is at-2.5V (vs. Pb/PbF)2) A metal element which is not fluorinated or defluorinated at the above potential, wherein the metal fluoride containing the M2 element and the F element has a fluoride ion conductivity of 1X 10 at 200 ℃-4And more than S/cm.
According to the present disclosure, since the negative electrode layer contains the metal of the M1 element and the metal fluoride including the M2 element and the F element, the metal of the M1 element and the metal fluoride are dispersed at an atomic level, and thus a fluoride ion battery having good capacity characteristics can be manufactured.
In the above disclosure, it is preferred that the M1 element be at-1.5V (vs. Pb/PbF)2) The following potentials are those at which fluorination and defluorination of the metal elements occur. This is because the battery voltage can be increased.
In the above disclosure, it is preferable that the M1 element has at least one of La element and Ce element.
In the above disclosure, it is preferable that the M2 element has two or more metal elements.
In the above disclosure, it is preferable that the M2 element has at least one of a Ca element, a Ba element, a Li element, a Sr element, and a Y element.
Effects of the invention
The fluoride ion all-solid-state battery of the present disclosure achieves an effect of having good capacity characteristics.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a fluoride ion all-solid-state battery of the present disclosure.
FIG. 2 is a graph showing the results of using LaF3A schematic cross-sectional view for explaining the charging reaction of the fluoride ion battery of (1).
Fig. 3 is a schematic cross-sectional view illustrating a charging reaction of the fluoride ion battery of the present disclosure.
FIG. 4 shows a graph of La0.9Ba0.1F2.9A schematic cross-sectional view for explaining the charging reaction of the fluoride ion battery of (1).
Fig. 5 is a schematic cross-sectional view illustrating a charging reaction of a fluoride ion battery using a negative electrode mixture.
Fig. 6 is a schematic cross-sectional view showing the structure of the measuring cell (セル) in example 1.
FIG. 7 shows charge and discharge curves of examples 1 and 2 and comparative examples 1 to 3.
Fig. 8 is the result of XRD measurement of example 2.
Fig. 9 is the result of XPS measurement of example 2.
Description of the reference numerals
1 Positive electrode layer
2 negative electrode layer
3 solid electrolyte layer
4 positive electrode current collector
5 negative electrode collector
10 fluoride ion all-solid-state battery
Detailed Description
The fluoride ion all-solid-state battery of the present disclosure will be described in detail below.
Fig. 1 is a schematic cross-sectional view illustrating a fluoride ion all-solid-state battery according to the present disclosure, in which fig. 1(a) shows an initial state (a state before charging), fig. 1(b) shows a state after charging, and fig. 1(c) shows a state after discharging. The fluoride ion all-solid-state battery 10 shown in fig. 1(a) to (c) has a positive electrode layer 1, a negative electrode layer 2, a solid electrolyte layer 3 formed between the positive electrode layer 1 and the negative electrode layer 2, a positive electrode current collector 4 for collecting current from the positive electrode layer 1, and a negative electrode current collector 5 for collecting current from the negative electrode layer 2.
In the fluoride ion all-solid battery 10 shown in fig. 1(a), the negative electrode layer 2 contains a metal fluoride (M1M2F) containing M1 element, M2 element, and F element. When the fluoride ion all-solid battery 10 is charged, the metal fluoride (M1M2F) undergoes a defluorination reaction to form a metal (M1) of M1 element and a metal fluoride (M2F) containing M2 element and F element in an atomic-level dispersed state as shown in fig. 1 (b). Here, the metal of the M1 element (M1) is a simple metal (a simple substance M1) when the M1 element is a single metal element, and is an alloy (an alloy M1) when the M1 element has two or more metal elements. The metal of element M1 (M1) corresponds to the negative electrode active material in a charged state. On the other hand, the metal fluoride (M2F) has a predetermined fluoride ion conductivity and corresponds to a solid electrolyte. Note that, since the defluorination reaction occurs during charging, the F element content of M2F becomes smaller than that of M1M2F, but the expressions of M2F and M1M2F do not quantitatively express the F element content.
When the fluoride ion all-solid battery 10 shown in fig. 1(b) is discharged, as shown in fig. 1(c), a metal of M1 element (M1) undergoes a fluorination reaction to form a fluoride of M1 element (M1F). The fluoride of the M1 element (M1F) corresponds to a negative electrode active material in a discharge state. On the other hand, the metal fluoride (M2F) containing M2 element and F element does not react during discharge and exists as a solid electrolyte.
According to the present disclosure, since the negative electrode layer contains the metal fluoride including the M1 element, the M2 element, and the F element, a metal (active material) of the M1 element and a metal fluoride (solid electrolyte) including the M2 element and the F element can be formed in a state of being dispersed at an atomic level in the negative electrode layer at the time of charging. On the other hand, since the electron conductivity of the metal of the element M1 is high, the fluoride ion conductivity of the metal fluoride containing the element M2 and the element F is high, and both are dispersed at the atomic level, a fluoride ion battery having good capacity characteristics can be obtained.
In particular, in the present disclosure, the negative electrode layer after charging contains a metal of the M1 element and a metal fluoride including the M2 element and the F element, and has a structure in which both are dispersed at the atomic level. In such a negative electrode layer, a very good electron conduction path and fluoride ion conduction path are formed, and the electrode reaction can be promoted, so that a fluoride ion all-solid battery having good capacity characteristics can be obtained. The reason for the dispersion at the atomic level is that, at the time of charging, fluoride ions are desorbed from the metal fluoride (M1M2F), while the M1 element and the M2 element, which are metal elements (cations), are immobilized.
In addition, in the present disclosure, since the metal of the M1 element (M1) and the metal fluoride containing the M2 element and the F element (M2F) can be dispersed at the atomic level, fluoride ion conductivity can be ensured even if the proportion of the metal fluoride (M2F), i.e., the solid electrolyte, in the negative electrode layer is small. Therefore, the ratio of the metal (M1) of the M1 element, that is, the negative electrode active material in the negative electrode layer can be increased, and the capacity of the negative electrode layer can be increased. Therefore, in the present disclosure, the capacity characteristics of the negative electrode layer can be made good.
In the present disclosure, a metal (M1) that is an M1 element and a metal fluoride (M2F) are formed (phase-separated) from the metal fluoride (M1M2F) at the time of charging. Specifically, since the fluorination and defluorination potential of the M1 element is higher than that of the M2 element, if the potential of the negative electrode layer is lowered at the time of charging, the metal (M1) of the M1 element is generated from the metal fluoride (M1M2F), and the metal fluoride (M2F) remains.
The negative electrode layer of the present disclosure uses a metal fluoride (e.g., LaF) containing one metal element3) The capacity characteristics of the battery can be dramatically improved as compared with the negative electrode layer of (1). Here, the reason why sufficient capacity characteristics cannot be obtained in a battery using the negative electrode layer is presumed as follows. Using LaF as follows3The case of the negative electrode layer will be described as an example. Here, preferably, LaF at the time of charging3The defluorination reaction of (3) proceeds uniformly in the thickness direction of the negative electrode layer 2 from the negative electrode current collector 5 side. However, actually, as shown in fig. 2(a), the defluorination reaction proceeds unevenly from the negative electrode current collector 5 side in the thickness direction of the negative electrode layer 2, and La simple substance (La) is generated unevenly (locally). Further, it is presumed that LaF is generated as shown in FIG. 2(b) because the reaction proceeds unevenly3The state of remaining in La simple substance. It is presumed that the fluoride ion is converted to LaF covered with La simple substance3Whereby the LaF is cut off3It becomes impossible to perform further charge reaction. Therefore, unreacted LaF was presumed to be present3Remains in the negative electrode layer, whereby the charge capacity becomes low. It is also presumed that the discharge capacity is also reduced along with this.
In contrast, the negative electrode layer in the present disclosure contains a metal fluoride including an M1 element, an M2 element, and an F element. Hereinafter, a case where a LaCaBaF compound (M1 ═ La, M2 ═ Ca, and Ba) is used as a metal fluoride will be described as an example. In the present disclosure, as shown in fig. 3(a), a La simple substance (La) and a CaBaF compound (for example, CaBaF) are formed in a highly dispersed state from a LaCaBaF compound at the time of charging4). Therefore, as shown in fig. 3(a), even when the defluorination reaction is not uniformly performed, the unreacted metal fluoride (LaCaBaF compound) can be supplied with fluoride ions. Therefore, as shown in fig. 3(b), it is assumed that unreacted metal fluoride (LaCaBaF compound) hardly remains in the negative electrode layer 2. Therefore, it is presumed that a good charge capacity and discharge capacity are obtained.
As shown in comparative example 2 (FIG. 4) described later, the negative electrode layer was made of La0.9Ba0.1F2.9Formation of La (elemental metal) and BaF2In the case of (metal fluoride), when the fluoride ion conductivity of the obtained metal fluoride is low, that is, when the obtained metal fluoride has a low ionic conductivityEven when the obtained metal fluoride does not function as a solid electrolyte, good capacity characteristics cannot be obtained. In this case, it is presumed that the metal fluoride functions as an insulator. That is, in the present disclosure, the metal fluoride including the M2 element and the F element has a predetermined fluoride ion conductivity and functions as a solid electrolyte, and thus a fluoride ion all-solid battery having good capacity characteristics can be obtained.
In addition, a negative electrode layer using a negative electrode mixture material in which a powdery negative electrode active material and a powdery solid electrolyte are mixed will also be discussed. In the case where the negative electrode mixture is used, it is presumed that the fluoride ion conduction path cutoff can be suppressed by adding the solid electrolyte 3a in a powder form even when the defluorination reaction occurs unevenly, as shown in fig. 5. However, in the negative electrode layer using the negative electrode mixture, it is difficult to ensure a fluoride ion conduction path in the entire negative electrode layer by a small amount of the solid electrolyte. In addition, if the solid electrolyte is added to such an extent that the fluoride ion conduction path of the entire negative electrode layer can be secured, there is a fear that the proportion of the negative electrode active material in the negative electrode layer becomes relatively small, and therefore the capacity of the negative electrode layer itself becomes low. Further, in the negative electrode mixture, since a conductive material is often added to ensure electron conductivity, there is a concern that the capacity of the negative electrode layer itself may be lowered. In contrast, in the present disclosure, a metal (active material) of the M1 element and a metal fluoride (solid electrolyte) containing the M2 element and the F element may be formed in an atomic-level dispersed state in the negative electrode layer at the time of charging. As a result, the proportion of the metal (active material) of the M1 element in the negative electrode layer can be increased, and the capacity of the negative electrode layer can be increased.
The following describes each configuration of the fluoride ion all-solid-state battery of the present disclosure.
1. Negative electrode layer
The negative electrode layer in the present disclosure contains a metal fluoride. The negative electrode layer may or may not contain a conductive material other than the metal fluoride, but the latter is preferable. This is because high capacity quantization can be achieved.
(1) Metal fluorides
The metal fluoride preferably contains M1 element, M2 element and F element.
(i) M1 element
The M1 element is a metal element having a higher potential for fluorination and defluorination (fluorination and defluorination potentials) than the M2 element described later. The fluorination and defluorination potential of the M1 element is typically-2.5V (vs. Pb/PbF)2) Above, it may be-2.4V (vs. Pb/PbF)2) Above this, it may be-2.3V (vs. Pb/PbF)2) The above. The fluorination and defluorination potential of the M1 element is, for example, -1.5V (vs. Pb/PbF)2) Hereinafter, it may be-1.6V (vs. Pb/PbF)2) Hereinafter, the concentration may be-1.7V (vs. Pb/PbF)2) The following.
Here, the "potentials at which the metal element is fluorinated and defluorinated" mean electrochemical potentials at which the metal element is fluorinated and defluorinated. Specifically, the "potential at which the metal element is fluorinated and defluorinated" is an equilibrium reaction (M + F) between the metal element (M element) and the F element－←→MF+e－) The thermodynamic value is a value inherent to each metal element.
In the fluoride ion all-solid-state battery of the present disclosure, it is assumed that the F element directly reacts with the metal element both at the time of charge and at the time of discharge, and therefore the fluorination reaction and the defluorination reaction of the metal element theoretically occur at the same potential, that is, at a potential determined by the equilibrium reaction.
The "potential at which the metal is fluorinated and defluorinated" can be determined by Cyclic Voltammetry (CV), for example.
Examples of the M1 element include at least one of lanthanides such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, Al, Be, Mg, Na, K, Rb, Cs, Sc, Th, Hf, Ti, and Zr. The M1 element may be only one metal element, or may have two or more metal elements. In the present disclosure, at least one of La element and Ce element is more preferable. The proportion of La element in the total of M1 elements may be 50 mol% or more, 70 mol% or more, 90 mol% or more, or 100 mol% (La element only). The same applies to the proportion of Ce element in all M1 elements and the proportion of La element and Ce element in all M1 elements.
As described above, the M1 element becomes a metal of the M1 element (M1 simple substance, M1 alloy) after charging.
(ii) M2 element
The M2 element is a metal element that undergoes fluorination and defluorination at a lower potential than the M1 element. That is, the fluorination and defluorination of the M2 element did not occur at the fluorination and defluorination potential of the M1 element. Specifically, the M2 element is at-2.5V (vs. Pb/PbF)2) Metal elements which are not fluorinated or defluorinated at the above potential. The fluorination and defluorination potential of the M2 element is generally less than-2.5V, and may be-2.7V (vs. Pb/PbF)2) Hereinafter, it may be-2.8V (vs. Pb/PbF)2) The following. Further, the fluorination and defluorination potential of the M2 element is, for example, -3.5V (vs. Pb/PbF)2) The above. The difference between the fluorination and defluorination potentials of the element M1 and the element M2 is, for example, preferably 0.05V or more, and preferably 0.1V or more.
The element M2 is a fluoride having an ion conductivity of 1X 10 at 200 ℃ in the case of forming a fluoride-4Metal elements of S/cm or more. More specifically, the element M2 is a metal element that can obtain a predetermined fluoride ion conductivity when a metal fluoride (M2F) containing the element M2 and the element F is formed. For example, Ca in examples described later1-xBaxF2(0 < x < 1) fluoride ion conductivity at 200 ℃ of 1X 10-4And more than S/cm. The fluoride ion conductivity at 200 ℃ may be 5X 10-4S/cm or more, and may be 1X 10-3And more than S/cm.
The fluoride ion conductivity referred to above is the fluoride ion conductivity in the compact of the M2 element, the fluoride (M2F) thereof, in the negative electrode layer. The specific measurement method is as follows. First, at
Figure BDA0001488289800000091
A ceramic cylinder made of マコール (9) was charged with 200mg of fluoride (M2F) powder and passed through a tube at 1 ton/cm2The uniaxial pressing of (2) is molded into a sheet shape. Then, acetylene black (current collector) was laminated on both surfaces of the sheet at a rate of 4 ton/cm2Is pressed. The pressed laminate was fastened by bolts with a torque of 6N · m. Thus, an evaluation cell was obtained. The measurement environment was set to 10-3AC impedance was measured under vacuum at 200 ℃ under Pa. Frequency 10 for AC impedance measurement6Hz～10-2Hz, the voltage amplitude was set to 50 mA. Thus, fluoride ion conductivity at 200 ℃ was obtained.
Examples of the metal element of the M2 element include at least one of Ca element, Ba element, Li element, Sr element, and Y element. The M2 element may be only one metal element or may have two or more metal elements, but the latter is more preferable. When the M2 element has two or more metal elements, a preferable combination includes, for example, Ca element and Ba element.
(iii) Metal fluorides
The metal fluoride preferably contains M1 element, M2 element and F element. The metal fluoride is typically a solid solution. The metal fluoride may contain only M1 and M2 elements, or may further contain other metal elements, although the former is more preferable, containing at least M1 element and M2 element as metal elements. The total ratio of the M1 element and the M2 element in all the metal elements in the metal fluoride is, for example, 90 mol% or more. On the other hand, the proportion of the M1 element to the total of the M1 element and the M2 element is, for example, preferably 75 mol% or more, and more preferably 80 mol% or more. The content of the element M1 is, for example, 95 mol% or less.
The metal fluorides preferably have the formula, for example, from M1xM2(1-x)Fy(x is more than or equal to 0.75 and less than or equal to 0.95, and y is a real number more than 0). Here, the value of x is preferably 0.75 or more, and may be 0.8 or more. The value of x is, for example, 0.95 or less.
The value of y is generally a real number greater than 0, and is preferably determined stoichiometrically according to the valences of the M1 element and the M2 element in the metal fluoride. For example, the value of y may be greater than 2, 2.5 or more, or 2.75 or more. The value of y may be, for example, less than 3, 2.95 or less, or 2.9 or less.
The metal fluoride preferably has peaks observed at positions of 2 θ ═ 24.20 ° ± 0.50 °, 24.80 ° ± 0.50 °, 27.64 ° ± 0.50 °, 34.90 ° ± 0.50 °, 43.63 ° ± 0.50 °, 44.71 ° ± 0.50 °, 49.50 ° ± 0.50 °, 50.48 ° ± 0.50 °, 52.41 ° ± 0.50 ° in an X-ray diffraction measurement using CuK α rays. These peak positions are based on La described later0.9Ca0.06Ba0.04F2.9The peak position of (A) is defined within a range of + -0.50 DEG with respect to La0.9Ca0.06Ba0.04F2.9A similar crystalline phase. The range of the peak position may be ± 0.30 ° or ± 0.10 °.
On the other hand, for example, the negative electrode layer after charging contains a metal of M1 element (M1) and a metal fluoride containing M2 element and F element (M2F), and the metal of M1 element (M1) and the metal fluoride (M2F) are dispersed at the atomic level. The dispersion at the atomic level can be confirmed by observation with a Transmission Electron Microscope (TEM), for example. When the negative electrode layer contains a metal of the M1 element and a metal fluoride containing the M2 element and the F element, the ratio of the M1 element to the total of the M1 element and the M2 element is, for example, preferably 75 mol% or more, and more preferably 80 mol% or more. The content of the element M1 is, for example, 95 mol% or less.
Examples of the method for producing the metal fluoride include a method in which raw materials serving as an M1 element source, an M2 element source, and an F element source are mixed and heat-treated. Examples of the source of the element M1 include a metal fluoride containing an element M1. Examples of the source of the element M2 include a metal fluoride containing an element M2. The heat treatment temperature is, for example, preferably in the range of 800 to 1100 ℃ and more preferably in the range of 900 to 1000 ℃. The heat treatment atmosphere may be, for example, an inert gas (e.g., Ar gas) atmosphere.
(2) Negative electrode layer
The negative electrode layer in the present disclosure contains the above-described metal fluoride. The negative electrode layer preferably includes a metal fluoride mainly containing M1 element, M2 element, and F element. The content of the metal fluoride in the negative electrode layer is, for example, 70% by weight or more, may be 90% by weight or more, and may be 100% by weight. The negative electrode layer preferably contains a metal of M1 element and a metal fluoride containing M2 element and F element as main components. The total content of the metal of the M1 element and the metal fluoride in the negative electrode layer is, for example, 70 wt% or more, 90 wt% or more, or 100 wt%.
The thickness of the negative electrode layer varies greatly depending on the composition of the battery, and is not particularly limited.
2. Positive electrode layer
The positive electrode layer in the present disclosure is a layer containing a positive electrode active material that undergoes a fluorination reaction during discharge and a defluorination reaction during charge. The positive electrode active material is a material that undergoes fluorination and defluorination at a higher potential than the M1 element in the negative electrode layer. Specifically, the positive electrode active material is preferably 0V (vs. Pb/PbF)2) The above potentials are fluorinated and defluorinated.
Examples of the positive electrode active material include a metal active material containing a metal element and a carbon active material containing a carbon element. Examples of the metal active material include a simple metal or an alloy of a metal element that is fluorinated and defluorinated at a higher potential than that of M1. Examples of the metal element used for the metal active material include at least one of a Pb element, a Cu element, an Ag element, an Mn element, an Fe element, a Ni element, a Co element, a W element, a Bi element, a Sn element, an Au element, a Pt element, a Mo element, a Cr element, a Pd element, and a Tl element. When the metal active substance is an alloy, it is preferable that the metal element (metal element a) having the highest fluorination potential and defluorination potential among the plurality of metal elements is the main component of the alloy. The proportion of the metal element a in the alloy may be 50 mol% or more, may be 70 mol% or more, and may be 90 mol% or more. Examples of the carbon active material include graphite and graphene.
Examples of the shape of the positive electrode active material include a particle shape and a film shape.
The thickness of the positive electrode layer greatly varies depending on the battery configuration, and is not particularly limited. The positive electrode layer can also function as a positive electrode current collector.
3. Solid electrolyte layer
The solid electrolyte layer in the present disclosure is a layer formed between the positive electrode layer and the negative electrode layer and containing a solid electrolyte.
The reduction potential of the solid electrolyte used for the solid electrolyte layer is lower than the fluorination and defluorination potentials of the M1 element. The reduction potential of the solid electrolyte is usually-2.5V (vs. Pb/PbF)2) Hereinafter, it may be-2.7V (vs. Pb/PbF)2) Hereinafter, it may be-2.8V (vs. Pb/PbF)2) The following. The reduction potential of the solid electrolyte may be, for example, -3.5V (vs. Pb/PbF)2) The above. The reduction potential of the solid electrolyte can be determined by Cyclic Voltammetry (CV), for example.
The fluoride ion conductivity of the solid electrolyte at 200 ℃ is preferably 1X 10-4S/cm or more, and may be 5X 10-4S/cm or more, and may be 1X 10-3And more than S/cm. The fluoride ion conductivity of the solid electrolyte can be determined by an ac impedance method. An example of such a solid electrolyte is a metal fluoride (M2F) containing M2 element and F element.
The thickness of the solid electrolyte layer in the present disclosure is not particularly limited, and varies greatly depending on the structure of the battery.
4. Other constitution
The fluoride ion all-solid-state battery of the present disclosure has at least the negative electrode layer, the positive electrode layer, and the solid electrolyte layer described above. In the present disclosure, a positive electrode current collector that performs current collection of the positive electrode layer and a negative electrode current collector that performs current collection of the negative electrode layer may be further provided. The shape of the current collector may be, for example, a foil shape.
The fluoride ion all-solid-state battery of the present disclosure preferably has a control portion that controls charging. The control unit is preferably a control unit that controls charging so that the potential of the negative electrode layer becomes a potential at which M1 element is defluorinated and M2 element is not defluorinated. In the present disclosure, it is preferable to control the potential of the negative electrode layer so as not to change at the time of chargingObtaining the product of which the voltage is lower than-2.5V (vs. Pb/PbF)2). In addition, it is preferable to control the potential of the negative electrode layer so that it becomes-1.5V (vs. Pb/PbF) during charging2) The following.
Examples of the Control Unit include an ECU (Electronic Control Unit) and a PCU (Power Control Unit). An ecu (electronic Control unit) instructs the PCU to charge and discharge (for example, start instruction or stop instruction) based on a request from the outside (for example, a request for charging or discharging) and the voltage and current of the fluoride ion all-solid-state battery. The PCU supplies power to the load during discharging and receives power from the power supply during charging.
5. Fluoride ion all-solid-state battery
The fluoride ion all-solid battery of the present disclosure has at least a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer. In the present disclosure, for example, in an initial state, the negative electrode layer contains a metal fluoride containing an M1 element, an M2 element and an F element, and the M1 element is at-2.5V (vs. Pb/PbF)2) The above metal element which is fluorinated and defluorinated at the above potential, wherein the above M2 element is at-2.5V (vs. Pb/PbF)2) A metal element which is not fluorinated or defluorinated at the above potential, wherein the M2 element has a fluoride ion conductivity of 1X 10 at 200 ℃ when the fluoride is formed-4Metal elements of S/cm or more. On the other hand, for example, after charging, the negative electrode layer contains a metal of M1 element and a metal fluoride containing M2 element and F element, the metal of M1 element and the metal fluoride are dispersed at an atomic level, and the M1 element is-2.5V (vs. Pb/PbF)2) The above metal element which is fluorinated and defluorinated at the above potential, wherein the above M2 element is at-2.5V (vs. Pb/PbF)2) A metal element which is not fluorinated or defluorinated at the above potential, wherein the metal fluoride containing the M2 element and the F element has a fluoride ion conductivity of 1X 10 at 200 ℃-4And more than S/cm.
The fluoride ion all-solid-state battery of the present disclosure may be a primary battery or a secondary battery, and among them, a secondary battery is preferable. This is because repeated charging and discharging is possible, and is useful as a vehicle-mounted battery, for example. The primary battery also includes the use of a secondary battery (use for the purpose of discharging only once after charging). Examples of the shape of the fluoride ion all-solid-state battery of the present disclosure include a coin shape, a laminate shape, a cylindrical shape, and a rectangular shape.
Note that the present disclosure is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present disclosure and achieving the same operational effects are included in the technical scope of the present disclosure.
Examples
Hereinafter, the present disclosure will be described in further detail with reference to examples.
[ example 1]
(Synthesis of Metal fluoride)
Weighing LaF3、CaF2、BaF2To yield, in terms of molar ratios, La: ca: ba 76:9:15, mixed with a planetary ball mill at 600rpm for 12 hours. The ball-milled powder was fired at 900 ℃ for 4 hours in an Ar atmosphere, whereby La was obtained0.76Ca0.09Ba0.15F2.76. When the firing temperature is 850 ℃ or lower, impurities having a fluorite structure may be easily generated, and when the firing temperature exceeds 1000 ℃, impurities having an oxide structure may be easily generated. Therefore, the firing temperature is preferably in the range of 900 to 1000 ℃, more preferably 900 ℃.
(preparation of measurement cell)
Weigh 150mg of Ca0.6Ba0.4F2As a solid electrolyte. Weighing the solid electrolyte at 1 ton/cm2Then, uniaxial pressing was performed to obtain a solid electrolyte layer (pressed powder molded body). 10mg of La was laminated on the obtained solid electrolyte layer0.76Ca0.09Ba0.15F2.76At 1 ton/cm2The negative electrode layer was obtained by uniaxial press molding. As a negative electrode current collector, 3mg ofAcetylene black.
Laminating Pb foil as positive electrode layer on the surface opposite to the solid electrolyte layer at 4 ton/cm2Uniaxial press molding was performed to obtain a unit cell. The obtained unit elements were fastened together at 6 N.m, to obtain a measurement cell. Fig. 6 shows the structure of the measuring unit. The positive electrode layer also functions as a positive electrode current collector.
[ example 2]
Weighing LaF3、CaF2、BaF2To yield, in terms of molar ratios, La: ca: a metal fluoride was obtained in the same manner as in example 1, except that Ba was 90:6: 4. The composition of the obtained metal fluoride is La0.9Ca0.06Ba0.04F2.9. A measurement cell was obtained in the same manner as in example 1, except that the obtained metal fluoride was used.
Comparative example 1
Except that LaF heat-treated at 800 deg.C is used3A measurement cell was obtained in the same manner as in example 1, except that the metal fluoride was used.
Comparative example 2
Weighing LaF3And BaF2A metal fluoride was obtained in the same manner as in example 1, except that the molar ratio was changed to 90: 10. The composition of the obtained metal fluoride is La0.9Ba0.1F2.9. A measurement cell was obtained in the same manner as in example 1, except that the obtained metal fluoride was used.
Comparative example 3
La0.9Ba0.1F2.9And Ca0.6Ba0.4F2The resultant was mixed in a mortar at a weight ratio of 9:1 to prepare a negative electrode mixture. The element ratio of this mixture was 76:9:15 in terms of molar ratio La: Ca: Ba as in example 1.
A cell for measurement was obtained in the same manner as in example 1, except that the obtained negative electrode mixture was used.
[ evaluation ]
(Charge and discharge test)
The cell for measurement was subjected to a charge/discharge test. The charge and discharge conditions are 1 × 10-3Heating the cell for measurement to 200 ℃ in a vacuum atmosphere of Pa or less, and applying-2.5V (vs. Pb/PbF)2)～－1.5V(vs.Pb/PbF2) Range (C) and charge-discharge rate C/30. The results are shown in fig. 7 and table 1. The charge-discharge curve of fig. 7 shows the charge-discharge curve of the negative electrode layer.
TABLE 1
Figure BDA0001488289800000151
As shown in fig. 7 and table 1, in examples 1 and 2, it was confirmed that the charge capacity per weight of the negative electrode layer was a high value exceeding 300 mAh/g. In examples 1 and 2, it was confirmed that the discharge capacity per weight of the negative electrode layer was a high value exceeding 200 mAh/g.
In examples 1 and 2, it is assumed that fluoride ions are desorbed from the LaCaBaF compound in the negative electrode layer at the time of initial charging, and a state is formed in which the La simple substance and the CaBaF compound are dispersed at the atomic level. Further, it is presumed that the La simple substance is fluorinated (functions as an active material), and a small amount of the CaBaF compound functions as a solid electrolyte, thereby improving the charge capacity and discharge capacity.
On the other hand, it was confirmed that in comparative example 1, the charge capacity and the discharge capacity were lower than those in examples 1 and 2. In comparative example 1, fluoride ions were derived from LaF during charging3Only La is generated after detachment. In comparative example 1, it is estimated that the generation reaction of La in the negative electrode layer (defluorination reaction) proceeds unevenly, and therefore the fluoride ion conduction path in the negative electrode layer is interrupted, and the reaction stops halfway.
In addition, it was confirmed that in comparative example 2, the charge capacity and the discharge capacity were lower than those in examples 1 and 2. In comparative example 2, it is presumed that La was formed in the negative electrode layer at the time of initial charging0.9Ba0.1F2.9Form La simple substance and BaF2。BaF2Fluoride ion conductivity at 200 ℃ is very low 1X 10-9Since S/cm is about, it is estimated that a good charge capacity and discharge capacity cannot be obtained.
In comparative example 3, it was confirmed that the charge capacity and the discharge capacity were lower than those of examples 1 and 2. In addition, it was confirmed that in comparative example 3, the charge capacity and the discharge capacity were higher than those in comparative example 2. In comparative example 3, Ca was added0.6Ba0.4F2(solid electrolyte) powder with La0.9Ba0.1F2.9The powder of (3) was mixed so as to make the composition ratio consistent with that of example 1, but it is presumed that the dispersibility of the solid electrolyte powder in the negative electrode layer is poor, and thus the fluoride ion conduction path cannot be sufficiently secured.
From the above results, it was confirmed that in examples 1 and 2, the capacity characteristics of the fluoride ion all solid-state battery and the capacity characteristics of the negative electrode layer were improved as compared with comparative examples 1 to 3.
(XRD measurement)
The metal fluoride of example 2 in the initial state, after the initial charge and after the initial discharge was subjected to powder XRD measurement. The metal fluoride was charged into an XRD glass holder, and measured at a scanning rate of 10 °/min using CuK α rays at 2 θ of 10 ° to 80 °. The results are shown in FIG. 8.
In the metal fluoride in the initial state, peaks were observed at positions of 2 θ ═ 24.20 °, 24.80 °, 27.64 °, 34.90 °, 43.63 °, 44.71 °, 49.50 °, 50.48 °, and 52.41 °. All the diffraction peaks belong to La0.9Ca0.06Ba0.04F2.9Peak of (2).
In the charged metal fluoride, La0.9Ca0.06Ba0.04F2.9The peak of (2) was small, and a peak ascribed to La and a peak ascribed to the solid electrolyte Ca were observed(1-x)BaxF2(0 < x < 1) (CaBaF compound). After the discharge, the peak ascribed to LaF was observed as the disappearance of the La simple substance3And a peak ascribed to the CaBaF compound. To be described, in La0.9Ca0.06Ba0.04F2.9Substantially the same positionLaF was observed3Peak of (2).
From the results, it was confirmed that: in the negative electrode layer using the metal fluoride of example 2, the metal fluoride was separated into La and a CaBaF compound during initial charging, and failed to return to La after initial discharging occurred0.9Ca0.06Ba0.04F2.9Irreversible reaction. That is, it was confirmed that in example 2, the metal fluoride containing the M1 element, the M2 element, and the F element phase-separated into the metal of the M1 element and the metal fluoride containing the M2 element and the F element at the time of initial charge, and the metal of the M1 element phase-separated at the time of initial discharge was fluorinated to form the metal fluoride containing the M1 element (M1F).
(XPS measurement)
XPS measurement was performed on the metal fluoride of example 2 in an initial state, after initial charge, and after initial discharge, and peaks of La element, Ca element, Ba element, and F element were measured. The results are shown in FIGS. 9(a) to (e). As shown in fig. 9(a) to (e), only La element was observed before and after charge and discharge, and peak shift and peak intensity change were observed in association with the redox reaction.

Claims (9)

1. A fluoride ion all-solid battery comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer,
the negative electrode layer contains a metal fluoride including an M1 element, an M2 element and an F element,
the M1 element is at-2.5V vs. Pb/PbF2Metal elements fluorinated and defluorinated at the above potentials,
the M2 element is at-2.5V vs. Pb/PbF2Metal elements which are not fluorinated or defluorinated at the above potential,
when the element M2 is a fluoride, the fluoride ion conductivity at 200 ℃ is 1X 10-4S/cm or more, and the M2 element has two or more metal elements.
2. The fluoride ion all-solid battery of claim 1, wherein the metal fluoride has a chemical formula of M1xM2(1-x)FyThe composition is represented by x is more than or equal to 0.75 and less than or equal to 0.95, and y is a real number more than 0.
3. A fluoride ion all-solid battery comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer,
the negative electrode layer contains a metal of M1 element and a metal fluoride including M2 element and F element, the metal of M1 element and the metal fluoride being dispersed at an atomic level,
the M1 element is at-2.5V vs. Pb/PbF2Metal elements fluorinated and defluorinated at the above potentials,
the M2 element is at-2.5V vs. Pb/PbF2Metal elements which are not fluorinated or defluorinated at the above potential,
the metal fluoride containing the M2 element and the F element has a fluoride ion conductivity of 1X 10 at 200 ℃-4And more than S/cm.
4. The fluoride ion all-solid battery of any one of claims 1 to 3, wherein the M1 element is at-1.5V vs. Pb/PbF2The following potentials are those at which fluorination and defluorination of the metal elements occur.
5. The fluoride ion all-solid battery according to any one of claims 1 to 3, wherein the M1 element has at least one of a La element and a Ce element.
6. The fluoride ion all-solid battery according to claim 3, wherein the M2 element has two or more metal elements.
7. The fluoride ion all-solid battery according to any one of claims 1 to 3, wherein the M2 element is selected from a Ca element, a Ba element, a Li element, a Sr element, and a Y element.
8. The fluoride ion all-solid battery according to claim 4, wherein the M1 element has at least one of a La element and a Ce element.
9. The fluoride ion all-solid battery according to claim 4, wherein the M2 element is selected from the group consisting of a Ca element, a Ba element, a Li element, a Sr element, and a Y element.
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